Dirty Business - American Chemical Society



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February 2014

Teacher's Guide for

Going the Distance:

Searching for Sustainable Shoes

Table of Contents

About the Guide 2

Student Questions 3

Answers to Student Questions 4

Anticipation Guide 5

Reading Strategies 6

Background Information (teacher information) 8

Connections to Chemistry Concepts (for correlation to course curriculum) 21

Possible Student Misconceptions (to aid teacher in addressing misconceptions) 21

Anticipating Student Questions (answers to questions students might ask in class) 22

In-Class Activities (lesson ideas, including labs & demonstrations) 22

Out-of-class Activities and Projects (student research, class projects) 23

References (non-Web-based information sources) 24

Web Sites for Additional Information (Web-based information sources) 25

More Web sites on Teacher Information and Lesson Plans (sites geared specifically to teachers) 27

About the Guide

Teacher’s Guide editors William Bleam, Donald McKinney, Ronald Tempest, and Erica K. Jacobsen created the Teacher’s Guide article material. E-mail: bbleam@

Susan Cooper prepared the anticipation and reading guides.

Patrice Pages, ChemMatters editor, coordinated production and prepared the Microsoft Word and PDF versions of the Teacher’s Guide. E-mail: chemmatters@

Articles from past issues of ChemMatters can be accessed from a CD that is available from the American Chemical Society for $30. The CD contains all ChemMatters issues from February 1983 to April 2008.

The ChemMatters CD includes an Index that covers all issues from February 1983 to April 2008.

The ChemMatters CD can be purchased by calling 1-800-227-5558.

Purchase information can be found online at chemmatters

Student Questions

1. What is the focus of the branch of chemistry known as “green chemistry”?

2. The “green” shoes mentioned in the article are made of recycled materials. What benefit does this provide over using new materials?

3. Which chemicals has the PUMA company committed to phasing out of its products and supply chain?

4. Perfluorocarbons (PFCs) are used to make shoes and clothes waterproof. How does their chemical structure allow for this use?

5. What is a drawback to using perfluorocarbons (PFCs) in manufacturing?

6. Describe the alternative material used for the sole of the PUMA Re-Suede shoe.

7. What are useful guidelines to consider when designing a “green” product or redesigning an old product in an environmentally friendly way?

8. Which principles of green chemistry do the PUMA Re-Suede shoes meet?

Answers to Student Questions

1. What is the focus of the branch of chemistry known as “green chemistry”?

The branch of chemistry known as “green chemistry” focuses on reducing or eliminating substances that are harmful to human health and the environment.

2. The “green” shoes mentioned in the article are made of recycled materials. What benefit does this provide over using new materials?

Using recycled materials for the “green shoes” can provide two benefits:

a. It saves energy consumption.

b. It reduces carbon emissions.

3. Which chemicals has the PUMA company committed to phasing out of its products and supply chain?

PUMA has committed to phasing out long-chain fluorinated chemicals, or perfluorocarbons (PFCs).

4. Perfluorocarbons (PFCs) are used to make shoes and clothes waterproof. How does their chemical structure allow for this use?

Perfluorocarbons (PFCs) have a chemical structure that is nonpolar. Because nonpolar molecules do not bind with polar molecules, such as water, PFCs are insoluble in water, which can make materials waterproof.

5. What is a drawback to using perfluorocarbons (PFCs) in manufacturing?

A drawback to using perfluorocarbons (PFCs) in manufacturing is that they break down to form substances such as perfluorooctanesulfonic acid, a toxic chemical that remains in the environment and concentrates as it moves up the food chain.

6. Describe the alternative material used for the sole of the PUMA Re-Suede shoe.

The sole of the PUMA Re-Suede shoe uses an alternative material called Double-R Rice Rubber, a combination of natural rubber and rice husk waste.

7. What are useful guidelines to consider when designing a “green” product or redesigning an old product in an environmentally friendly way?

Useful guidelines to consider when designing a “green” product or redesigning an old product in an environmentally friendly way are the twelve principles of green chemistry.

8. Which principles of green chemistry do the PUMA Re-Suede shoes meet?

The PUMA Re-Suede shoes meet six of the green chemistry principles:

1) Prevent waste; 3) Less hazardous chemical synthesis; 4) Design safe chemicals; 6) Design for energy efficiency; 7) Use renewable feedstock; and 10) Design for degradation.

Anticipation Guide

Anticipation guides help engage students by activating prior knowledge and stimulating student interest before reading. If class time permits, discuss students’ responses to each statement before reading each article. As they read, students should look for evidence supporting or refuting their initial responses.

Directions: Before reading, in the first column, write “A” or “D,” indicating your agreement or disagreement with each statement. As you read, compare your opinions with information from the article. In the space under each statement, cite information from the article that supports or refutes your original ideas.

|Me |Text |Statement |

| | |“Green” shoes may be made from recycled materials. |

| | |Perfluorocarbons (PFCs) contain carbon, fluorine, and hydrogen atoms. |

| | |PFCs are waterproof because they are nonpolar. |

| | |PFCs break down into harmless chemicals when they are released into the environment. |

| | |Rice husk waste is incorporated into the soles of the shoes described in the article. |

| | |Green chemistry principles address energy issues as well as environmental issues. |

| | |Products designed using green chemistry principles should be created using large amounts of reagents. |

Reading Strategies

These matrices and organizers are provided to help students locate and analyze information from the articles. Student understanding will be enhanced when they explore and evaluate the information themselves, with input from the teacher if students are struggling. Encourage students to use their own words and avoid copying entire sentences from the articles. The use of bullets helps them do this. If you use these reading strategies to evaluate student performance, you may want to develop a grading rubric such as the one below.

|Score |Description |Evidence |

|4 |Excellent |Complete; details provided; demonstrates deep understanding. |

|3 |Good |Complete; few details provided; demonstrates some understanding. |

|2 |Fair |Incomplete; few details provided; some misconceptions evident. |

|1 |Poor |Very incomplete; no details provided; many misconceptions evident. |

|0 |Not acceptable |So incomplete that no judgment can be made about student understanding |

Teaching Strategies:

1. Links to Common Core Standards for writing:

a. Ask students to defend their position on sustainable choices, using information from the articles.

b. Ask students to revise one of the articles in this issue to explain the information to a person who has not taken chemistry. Students should provide evidence from the article or other references to support their position.

2. Vocabulary that is reinforced in this issue:

• Emulsion and emulsifiers

• Coalescence

• Green chemistry

• Joule

• Allotrope

• Hydrolysis

• Fermentation

3. To help students engage with the text, ask students what questions they still have about the articles. The articles about green chemistry (“Going the Distance: Searching for Sustainable Shoes” and “It’s Not Easy Being Green—Or Is It?”) may challenge students’ beliefs about sustainability.

Directions: As you read the article, complete the graphic organizer below to describe what you learned about green chemistry and sustainable shoes.

|3 |Your friends are discussing what to look for when buying new shoes. Write three new things you learned about buying |

| |“green” shoes from reading this article that you would like to share with your friends. |

| | |

| |1. |

| |2. |

| |3. |

|2 |Share two things you learned about chemistry from the reading the article. |

| | |

| |1. |

| |2. |

|1 |Did this article change your views about green chemistry? Explain in one sentence. |

|Contact! |Describe a personal experience about green chemistry principles that connects to something you read in the |

| |article—something that your personal experience validates. |

Background Information (teacher information)

More on shoe manufacture and design

Take a peek in someone’s closet and you’ll likely see at least a small collection of shoes—shoes for exercising, shoes for dressing up, boots for slushy weather, slippers for lounging around, all available in stores in an array of colors and styles to fit our individual tastes. Those who participate in sports may have shoes specific to their own activity, such as track shoes with spikes, basketball shoes that offer particular support, etc. We have shoes to fit many different situations, but the main purposes of shoes are to protect and support our feet. A history of shoes suggests this as well, from the earliest times:

There is much evidence that a foot covering was one of the first things made by our primitive ancestors. Necessity compelled them to invent some method of protecting their feet from the jagged rocks, burning sands, and rugged terrain over which they ranged in pursuit of food and shelter.

The history of human development shows that the importance of protecting the foot was early recognized [sic]. Records of the Egyptians, the Chinese and other early civilizations all contain references to shoes. The shoe is repeatedly mentioned in the Bible and the Hebrews used it in several instances with a legal significance, notably in binding a bargain. …

In its first form the shoe was just a simple piece of plaited grass or rawhide which was strapped to the feet. Among the relics of early Egyptians are some sandals made from plaited papyrus leaves, beautifully and artistically wrought. Records show that sandalmaking had become a well-recognized art early in the history of that country.

( shoes/history/history your shoes/history your shoes.htm)

To purchase a new pair of shoes in earlier years, one did not visit a store as we do, but rather made arrangements with a cobbler, who would make a custom pair of shoes fitted to the specific customer. For example, if you have read the book Farmer Boy from Laura Ingalls Wilder’s Little House on the Prairie series, set in the 1860s, a cobbler came to visit the home of the main character. (Wilder, L.I. Farmer Boy. New York: HarperCollins, 2008) Even though the children had grown out of their shoes earlier, the family had to wait for the cobbler to arrive. Each person who needed shoes needed to be there for him to properly measure their feet. From those measurements, he would whittle wooden lasts shaped like their feet, to properly fit and shape each new pair of shoes.

Eventually shoemaking processes evolved:

The nature of shoemaking in the U.S. changed right after the Revolutionary War. When the U.S. became a country in its own right, its newfound nationhood resulted in an increase in population, thereby increasing the demand for shoes and making it necessary to mass produce shoes. That was the beginning of the division of labor in shoe manufacturing. Instead of cobblers, shoemakers became craftspersons and began to specialize in making only one part of the shoe, such as making the sole or attaching the sole to the upper part of the shoe.

The gradual specialization of shoemaking increased as we entered the 19th century. Factories appeared that were dedicated to only one step of the shoe manufacturing process. Then, machines were used to stitch uppers to the soles rather than stitching the shoes by hand.

The advent of the Civil War increased the demand for shoes to be manufactured quickly and cheaply. The War also resulted in the first widespread standardizing of shoe sizes. Standardized sizes made it easier for soldiers to receive the correct size of army boots.

By the end of the 19th century, shoes could be made in a fraction of the time it took to make a pair of shoes by hand. By the 20th century, the shoe manufacturing process was divided into 150 distinct steps.

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Part of this evolution in manufacturing included the development of various machines that aided in the shoemaking process.

In 1845 the first machine to find a permanent place in the shoe industry came into use. It was the Rolling Machine, which replaced the lapstone and hammer previously used by hand shoemakers for pounding sole leather, a method of increasing wear by compacting the fibres.

This was followed in 1846 by Elias Howe's invention of the sewing machine. … In 1858, Lyman R. Blake, a shoemaker, invented a machine for sewing the soles of shoes to the uppers.

( shoes/history/history your shoes/history your shoes.htm)

These machines provided a start to the mechanization of the process. However, at least some steps still needed to be done by hand. At one point, people thought it would not be possible to ever make shoes completely by machine. An additional invention changed that.

Other inventors had managed to create machines to cut out the different parts of the shoe and to sew together the leather that made up the top, but the last and hardest part still had to be done by hand. Skilled shoemakers would shape the leather upper part of the shoe over a foot-shaped wooden mold called a last and then sew it onto the sole, or bottom, of the shoe. An expert shoe laster could make about fifty pairs of shoes a day. When [Jan] Matzeliger was thirty years old, he created a machine that could make 150 to 700 pairs a day…that’s fourteen times as many as a skilled person! …

Matzeliger’s shoe-lasting machine was so efficient that it cut the price of shoes in half after it went into production in 1885. Thanks to him, new shoes became much more affordable for average Americans.

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The requirements for a pair of shoes that provides sufficient support and protection is described in the ChemMatters article “Make the Shoe Fit,” which focused more specifically on shoes for basketball players. The article included the diagram below, along with a description of each part, and the materials used to construct them.

A shoe has six basic parts: the upper (top part); the tongue; the outsole (which grips surfaces and provides traction); the insole and midsole (which are the core); and the last (the form on which the shoe is made).

The upper is usually leather or synthetic leather … and it has air holes or mesh for ventilation. Most have extra eyelets so the shoes can be laced in different ways to tighten around your ankle or the top of your foot.

Some basketball shoes do not have tongues; they slide on your foot like a sock. The important characteristics for the tongue, if present, are that it feels comfortable and does not slip or rub during play. As a result, the tongue usually has foam backing.

The outsole of the shoe is important in traction. The heel resists wearing because of the strength of the rubber, which has carbon fibers added. The rest of the shoe is usually softer rubber carved with grooves and bumps to provide grip.

The shock absorption and arch support come from the insole. It is made from EVA polymers (ethylene–vinyl acetate copolymers) or polyurethane. These polymers are foams that are spongy and cushion the foot as it hits the floor.

In the midsole of athletic shoes, air and gel chambers are added for more shock absorption. In the past, athletic shoes contained sealed pockets of pressurized air to absorb shock; however, if the pocket was punctured, the shoe lost its shock absorption ability. … Another shoe manufacturer, Fila, uses cells of air in a rubber-like polymer to provide the necessary cushioning. These cells are open, leaving them unpressurized, so the air doesn’t escape if a cell is ruptured. …

The shoe last is the form on which the shoe is made. A board-lasted shoe contains a fiberboard shape that is attached to the upper, making a moderately stiff and stable shoe. For a flexible shoe, the last is slipped out of the shoe after the parts are stitched together. Some shoes have a combination last: The last in the front is taken out after assembly, but the board in the heel remains in place.

With time and use, though, the parts of the shoe wear out. The EVA or polyurethane foam will pack down and lose some of its cushioning character. The leather uppers begin to stretch with the foot instead of supporting it. It’s important to replace worn-out shoes before you injure yourself.

(Baxter, R. Make the Shoe Fit. ChemMatters 1999, 17 (1), pp 9–10)

In 2008, the American Chemical Society National Chemistry Week theme was titled “Having a Ball with Chemistry” and focused on sports. The Celebrating Chemistry newspaper included another illustration of the parts of a shoe and the materials used to make them.

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As seen in the description of some of the materials used, the properties of particular materials can be fine-tuned through chemistry to meet different needs. For example, it discusses controlling how rubber is made, to produce a harder or softer type of rubber.

More on “green” shoes

Nolte’s ChemMatters article focuses on the PUMA company’s efforts to use green chemistry principles to develop the PUMA Re-Suede shoes. Many other companies are also working to produce greener shoes, sports apparel, and many other products. For example, in its document “Shoe Industry Steps into Green Manufacturing,” the Daniel Green company, which makes slippers and casual shoes, discusses practices that it and other companies use. These include the use of wind and solar energy in manufacturing; converting waste products into usable energy; energy conserving machinery; green and recycled textiles such as recycled wool, recycled polyester, PET, organic cotton, bamboo, and hemp; green packaging made of recycled and post-consumer paper with soy ink; and the donation of overstock and outdated shoes to organizations that can make use of them. ()

The blog “Benvironment” discusses the availability of compostable shoes. These include shoes made by OneMoment, which claims their shoes biodegrade in six months. The blog describes these fairly thin shoes: “The design is apparently inspired by the indigenous peoples of the Amazon, who would paint the soles of their feet with natural latex for protection during the rainy season.” It also mentions OAT shoes: “The lining in the shoes is apparently embedded with saplings [actually a wildflower mix], so that soon after you’ve buried your stinky shoes in the soil they’ll turn into something rather lovely… whilst decomposing.” ()

Part of the application of green chemistry principles can mean thinking about a process or product in a new way. Shoes themselves are being re-imagined, as this description of an “origami shoe” illustrates:

For hundreds of thousands of people around the world, shoes aren’t something to collect—they’re actually so cost-prohibitive people can’t afford a single pair. Supplying poverty-stricken countries with shoes has been the focus of many a humanitarian effort, but few have gone beyond the Santa Claus gifting mindset to actually change the way they’re made, distributed and priced around the world.

But a new project from Horatio Yuxin Han, a recent graduate of the Pratt Institute, and his professor Kevin Crowley, is totally re-imagining how shoes could be manufactured. Called Unifold, Han used the principles of origami to build a cheap and relatively sturdy pair of shoes.

From a single piece of ethylene vinyl acetate (foam rubber), people can cut out a pattern and fold it up into a wearable pair of shoes. This eliminates the need for the expensive machinery that’s usually required to produce footwear. “I tried to figure out how to make them with the simplest tool possible,” explains Han. “With the Unifold, all you need is die-cut machine and a die, and then you could start a production line.”

The idea is that by simplifying the process, it not only reduces cost, but it localizes production, too. Han says the original focus of the project was not necessarily humanitarian, though with a few design and material tweaks, it certainly could be. Rather, the goal was more holistic: replace traditional manufacturing with a process that makes shoes less expensive and more accessible for people everywhere.

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The larger shoe companies are also making various changes to shoe designs. The article “Nike, Adidas, Puma, and rest in pursuit of ultimate sustainable shoe” from The Oregonian mentions several. () In 2012, Nike introduced a “Flyknit” shoe, which has an upper portion made from what looks like mesh. The company says the new design “eliminates one of the main culprits in shoe waste: discarded cuttings. … [I]t reduces waste because the one-piece upper does not use the multiple materials and material cuts used in traditional sports footwear manufacture.” The article also mentions Adidas, which with its “ForMotion soles,” has been able to “use 50 percent less material in production than for a typical sports shoe sole. The manufacturing processes also reduce or eliminate waste from other aspects of production.” It also mentions an overall benefit as shoes often become lighter through their re-designs: “And, as the entire sports footwear industry races to build a lighter running shoe, they're enjoying a side benefit in the process by reducing the fuel needed to ship the product to market. Several companies are reducing the sizes of the recyclable packaging for the same reason.”

Besides the shoes themselves, the processes used to make them are also undergoing green updates.

John Frazier, director of sustainable chemistry for Nike, offered another case study. But his company, in addition to creating a list of toxic substances to avoid actually went ahead and developed its own less toxic alternatives.

The first success story was environmentally preferred rubber. The company identified five chemicals in its original shoe rubber that are hazardous and worked to eliminate them.

In the original rubber, those five toxic chemicals made up 12 percent of the product by weight. The “green rubber” that Nike created has only one of the five chemicals in it, and that chemical makes up only 1 percent of the product by weight. …

The company was also successful in reducing zinc in its shoes. Using zinc meant emitting 340 grams of volatile organic compounds for every pair of shoes during the manufacturing process.

But Nike engineers discovered the zinc wasn’t really that essential to the shoes.

“It was there because it’s always been there,” said Frazier.

Nike engineers were able to remove 80 to 90 percent of the zinc in the shoe manufacturing process – reducing toxic emissions from 340 grams per pair in 1995 to 15 grams in 2006.

“It’s a huge difference,” Frazier said. “The consumer will never notice it, but the workers in the factories could tell the difference.”

It wasn’t easy to change those products, he said.

“These things are technical. You have to work with engineering teams. You have to make sure you don’t lose performance and make sure you don’t put yourself at a competitive disadvantage businesswise.”

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Many companies have made efforts to adjust some of their products to fit a greener viewpoint. However, although these efforts can create buzz among consumers and the media about green products and their benefits, the final decision about these products staying on the market comes down to consumers making actual purchases. Some products, although green, may be unpopular for other reasons and may not last long on the market. For example, Nike introduced the “Trash Talk” shoe in 2008. The upper portion of the shoe was made using pieces left over from the cutting of other shoes. Its life on the market was short-lived, surviving only until 2009. As another example, Patagonia manufactured the “Sugar & Spice” shoe. At the end of its useful life, the pieces of the shoe could be disassembled, making recycling the parts easy.

[It] features components that snap together and use minimal glues or cement. There are a couple of reasons why it never quite took off, theorizes Les Horne, senior product manager of Patagonia’s footwear division and one of the designers behind the disassembling shoe. “It’s great to have an eco-friendly story,” he told Ecouterre over the phone, “but the bottom line is people buy shoes for the aesthetics.” The Sugar & Spice, he admits, is on the heavy side, and the fact that it isn’t feminine (or conversely, masculine) enough doesn’t boost its case. “We went for a more unisex style, instead of making two different molds,” he says.

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A final part of applying the green chemistry process is what to do with shoes when they have no useful life left for wearing as the original shoes. Recycling shoes to use their components and materials as something else can be difficult, due to the complications of separating out the multiple types of materials that make up a shoe. This can be helped by looking at shoe design at the start, to make changes with the end of the shoes in mind that allow them to be more easily recycled. A recycling system has also been developed that overcomes the difficulties:

[S]cientists at Loughborough University in the UK announced last week that they have created and trialled "the world’s first comprehensive system for separating and recovering useful materials from old footwear."

The recycling system was developed at the university's Innovative Manufacturing and Construction Research Centre, and is the end result of a 10-year research program.

The process begins with shoes being manually sorted into broad categories (such as "trainers"), and having metal components such as eyelets removed. They are then automatically shredded and granulated, ending up as tiny fragments. Those fragments are sorted according to material, using three main methods – cyclonic separation, zigzag separation, and vibrating tables.

In the cyclonic separation process, a tornado-like vortex of air is created within an enclosed cylindrical chamber. The lightest fragments are picked up by that vortex and carried out of the chamber through an outlet tube in the top, while heavier fragments remain behind on the bottom.

Next, in the zigzag separation process, fragments are fed into the top of an enclosed column, and fall to the bottom by "zig-zagging" back and forth between alternating sloping platforms. Along the way, jets of air blowing in from the sides push the lighter fragments off to other receptacles, allowing only the heavier ones to reach the bottom.

Finally, when mixed fragments are placed on a sieve-like screen built into a vibrating table, the vibrations cause the smaller fragments to fall through the gaps in the screen, with the larger ones remaining on top.

By the time they get to the end of the line, the shoe fragments are sorted into four material types: leather, foam, rubber and other materials. The leather fragments could then be used to create sheets of bonded leather (real leather mixed with synthetic); the foam could go into items such as carpet underlays; the rubber could be used either in playground-surfacing materials or even in the soles of new shoes; and the mixed materials might find use as building insulation.

The university is now working with "major footwear manufacturers" to develop methods of designing footwear that would make it as recycling-friendly as possible. This could include using materials of very different densities, as doing so would make the separation process quicker and thus cheaper.

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You may already have come in contact with used and recycled Nike shoes. The company describes where you might find them:

Nike Reuse-a-Shoe takes worn out athletic shoes and grinds them down to create a new material called Nike Grind, which is used to make high-quality sports surfaces including courts, turf fields, tracks and more. Since 1990, we’ve transformed 28 million pairs of shoes and 36,000 tons of scrap material into Nike Grind for use in more than 450,000 locations around the world.

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PUMA also invites consumers to drop off old clothes and shoes (its own brand or others) in “Bring Me Back” bins. PUMA describes what happens then: “Almost every item gets a new life, whether it is re-worn, up-cycled for industrial use, or recycled and turned into raw materials to produce new products.” ()

More on green chemistry

One way to view the move toward green chemistry would be to say it has flipped the focus for hazardous wastes. Instead of being concerned with how to deal with hazardous materials and waste—what to do with the pollution generated by the use of these hazardous materials, how waste can be cleaned up after it is generated, how to deal with those who violate disposal laws, etc., green chemistry considers hazardous materials before they are even used and works toward replacing them with more benign alternatives. Instead of trying to contain pollution that using a hazardous material generates, is there a different material that that could be used to avoid generating the pollution in the first place? Instead of trying to clean up hazardous waste, what could be used to reduce or eliminate the waste? Green chemistry thinks about the process at the start and how it could be changed to positively affect the end, rather than just cleaning up the end.

The April 2003 ChemMatters Teacher’s Guide discusses the history of the beginning of the “Green Chemistry movement”:

The movement really began with the Pollution Prevention Act of 1990. It became a formal focus of the Environmental Protection Agency in 1991. Although something like 100 laws had been passed prior to the passage of the 1990 Act, these laws addressed the issues related to the cleanup of hazardous wastes, limiting the spread of pollutants, and assessing fines or penalties for violators.

The act encouraged both industry and academia to develop new technologies that would avoid the use of hazardous materials, and technologies that would replace those consuming vital and diminishing resources with processes consuming renewable resources.

(ChemMatters Teacher’s Guide. April 2003, p 12)

The American Chemical Society Green Chemistry Institute (ACS GCI) lists further key events in the history of green chemistry:

Early 1990’s

Green Chemistry gained its current standing as a scientific discipline as well as practical means to pollution prevention as the result of collaboration between the US government, Industry, and Academia. In the early 1990's, Paul Anastas, who was then the chief of the Industrial Chemistry Branch at the US EPA, moved forward the concept of Green Chemistry

Mid 1990's

Paul Anastas and John Warner developed the 12 Principles of Green Chemistry: a framework to help us think about how to prevent pollution when inventing new chemicals and materials. Paul Anastas and John Warner's work as founders of a new field called Green Chemistry, based on the productive collaboration of government and industry, was just beginning.

1993

A white paper entitled "Chemistry for a Clean World," published by the European Community's Chemistry Council in June, attracted a great deal of attention in Europe.

1995

President Bill Clinton established the Presidential Green Chemistry Challenge Awards to recognize chemical technologies that incorporate the principles of sustainable chemistry into chemical design, manufacture and use.

1996

The first Presidential Green Chemistry Challenge Awards winners were announced. The awards increased awareness of Green Chemistry in industry and government by annually acknowledging individuals, groups, and organizations in academia, industry, and the government for their innovations in cleaner, cheaper, smarter chemistry. This remains the only award given by the President of the United States specifically for work in chemistry.

1997

After more than a year of planning by individuals from industry, government, and academia, the Green Chemistry Institute (GCI) was incorporated in 1997 as a not-for-profit 501(c)3 corporation — devoted to promoting and advancing green chemistry.

1998

John Warner and Paul Anastas published the seminal book Green Chemistry: Theory and Practice, which gave a precise definition to Green Chemistry and enumerated the Twelve Principles fundamental to the science. The definition and principles have become the generally accepted guidelines for Green Chemistry. Since it was first published, the book has been re-printed in several languages. …

2001

GCI joined the American Chemical Society (ACS) in an increased effort to address global issues at the intersection of chemistry and the environment.

2006

The International Union of Pure and Applied Chemistry formed a special subcommittee on Green Chemistry and launched a bi-annual international conference. The first was held in Germany, the second in Russia, and the 2010 conference was slated for Canada.

2007

John Warner returned to industry to develop green technologies, partnering with Jim Babcock to found the first company completely dedicated to developing green chemistry technologies, the Warner Babcock Institute for Green Chemistry. The Institute was created with the mission to develop nontoxic, environmentally benign, and sustainable technological solutions for society.

Simultaneously, John Warner founded a non-profit foundation, Beyond Benign, to promote K-12 science education and community outreach.

2009

In May 2009, President Barack Obama nominated Paul Anastas to lead the U.S. Environmental Protection Agency's (EPA's) Office of Research and Development. The nomination is a decisive achievement for the adoption and advancement of the principles of Green Chemistry.

Today

The United States is just one of many countries that have green chemistry programs, centers, and educational initiatives. Others include Australia, China, Germany, India, Italy, the Netherlands, Spain, and the United Kingdom, to mention but a few.

ACS Green Chemistry Institute (ACS GCI)

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Paul Anastas, mentioned several times in the timeline above, including as one of the founders of green chemistry and co-author of the book that listed its twelve principles, published a related article “Design through the Twelve Principles of Green Engineering.” The twelve principles of green chemistry, as stated directly in the name, provide guidelines specific to chemistry. The principles of green engineering provide guidelines more related to the actual design process; for example, the design of the green shoes described in the Nolte article. The twelve principles of green engineering are:

|Principle 1: |Designers need to strive to ensure that all materials and energy inputs and outputs are as inherently |

| |nonhazardous as possible. |

|Principle 2: |It is better to prevent waste than to treat or clean up waste after it is formed. |

|Principle 3: |Separation and purification operations should be designed to minimize energy consumption and materials |

| |use. |

|Principle 4: |Products, processes, and systems should be designed to maximize mass, energy, space, and time |

| |efficiency. |

|Principle 5: |Products, processes, and systems should be “output pulled” rather than “input pushed” through the use of|

| |energy and materials. |

|Principle 6: |Embedded entropy and complexity must be viewed as an investment when making design choices on recycle, |

| |reuse, or beneficial disposition. |

|Principle 7: |Targeted durability, not immortality, should be a design goal. |

|Principle 8: |Design for unnecessary capacity or capability (e.g., “one size fits all”) solutions should be considered|

| |a design flaw. |

|Principle 9: |Material diversity in multicomponent products should be minimized to promote disassembly and value |

| |retention. |

|Principle 10: |Design of products, processes, and systems must include integration and interconnectivity with available|

| |energy and materials flows. |

|Principle 11: |Products, processes, and systems should be designed for performance in a commercial “afterlife.” |

|Principle 12: |Material and energy inputs should be renewable rather than depleting. |

(Anastas, P.T.; Zimmerman, J.B. Design Through the 12 Principles of Green Engineering. Environ. Sci. Technol. 2003, 37 (5), pp 94A–101A; see )

As the green chemistry movement has progressed through history, its growth has been aided by developments within the field of chemistry. For example, even a ChemMatters Teacher’s Guide published 15 years ago notes back then:

The U.S. Environmental Protection Agency (EPA) introduced green chemistry as a formal focus area in 1991. The significant growth of green chemistry since then has been driven by

• New knowledge of what is hazardous and what is innocuous,

• An ever-increasing ability of chemists to manipulate molecules to create only the substances they want, and

• Dramatically increased costs of using and disposing of hazardous substances.

(ChemMatters Teacher’s Guide. December 1999, p 12)

How much more of an increase in knowledge and technology has been achieved since that writing!

Students may wonder about some of the specific benefits of applying the principles of green chemistry, rather than a generalized statement: “It helps health and the environment.” The U.S. Environmental Protection Agency describes some specific benefits:

Human health:

• Cleaner air: Less release of hazardous chemicals to air leading to less damage to lungs

• Cleaner water: less release of hazardous chemical wastes to water leading to cleaner drinking and recreational water

• Increased safety for workers in the chemical industry; less use of toxic materials; less personal protective equipment required; less potential for accidents (e.g., fires or explosions)

• Safer consumer products of all types: new, safer products will become available for purchase; some products (e.g., drugs) will be made with less waste; some products (i.e., pesticides, cleaning products) will be replacements for less safe products

• Safer food: elimination of persistent toxic chemicals that can enter the food chain; safer pesticides that are toxic only to specific pests and degrade rapidly after use

• Less exposure to such toxic chemicals as endocrine disruptors

Environment:

• Many chemicals end up in the environment by intentional release during use (e.g., pesticides), by unintended releases (including emissions during manufacturing), or by disposal. Green chemicals either degrade to innocuous products or are recovered for further use

• Plants and animals suffer less harm from toxic chemicals in the environment

• Lower potential for global warming, ozone depletion, and smog formation

• Less chemical disruption of ecosystems

• Less use of landfills, especially hazardous waste landfills

Economy and business:

• Higher yields for chemical reactions, consuming smaller amounts of feedstock to obtain the same amount of product

• Fewer synthetic steps, often allowing faster manufacturing of products, increasing plant capacity, and saving energy and water

• Reduced waste, eliminating costly remediation, hazardous waste disposal, and end-of-the-pipe treatments

• Allow replacement of a purchased feedstock by a waste product

• Better performance so that less product is needed to achieve the same function

• Reduced use of petroleum products, slowing their depletion and avoiding their hazards and price fluctuations

• Reduced manufacturing plant size or footprint through increased throughput

• Increased consumer sales by earning and displaying a safer-product label (e.g., DfE labeling)

• Improved competitiveness of chemical manufacturers and their customers.

()

More on perfluorinated compounds

Looking deeper into the topic of long-chain fluorinated chemicals is made more difficult by the fact that these types of compounds are referred to by different names. Some terms include: perfluorinated chemicals, perfluorochemicals, perfluoroalkyls, perfluorinated alkyl acids, polyfluorinated chemicals, polyfluorinated compounds, polyfluoroalkyl substances. () Perfluorinated compounds as a group are succinctly described in the book Polyfluorinated Chemicals and Transformation Products, including their properties, uses in products, and the current state of knowledge about their use.

Perfluorinated compounds are a chemical family of all organic compounds consisting of a carbon backbone fully surrounded by fluorine and represent a large and complex group of organic substances with unique characteristics. They are used in several industrial branches, but they also occur in a large range of consumer products. Because of their extraordinary properties such as chemically inert, non-wetting, very slippery, nontoxic, nonstick, highly fire resistant, very high-temperature ratings, highly weather resistant, they are applied in fluoropolymer-coated cookware, sports clothing, extreme weather-resistant military uniforms, food handling equipment, medical equipment, motor oil additives, fire fighting foams, paint and ink as well as water-repellent products. Currently, the knowledge of the exact chemical compositions in articles and preparations of perfluorinated compounds is very limited. Since the exact composition of perfluorinated compounds in consumer products is mostly confidential, a range of analytical studies concerning the content of perfluorinated compounds in consumer products have been carried out over the past years with the intention to better understand the intentional and residual content and release of fluorinated substances from consumer products and their impact to health and the environment.

(Posner, S. (2012). Perfluorinated Compounds: Occurrence and Uses in Products. In T.P. Knepper & F.T. Lange (Eds.), Polyfluorinated Chemicals and Transformation Products, Springer, p 25. See - page-1)

Exposure to these compounds is thought to happen through contact with products that use them and through water or food that has been contaminated with the compounds. There are conflicting reports over their potential effects on the human body. A fact sheet produced by the National Institute of Environmental Health Sciences (part of the National Institutes of Health, U.S. Department of Health and Human Services) discusses these issues:

There is widespread wildlife and human exposure to several PFCs [perfluorinated chemicals], including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Both PFOA and PFOS are byproducts of other commercial products, meaning they are released into the environment when other products are made, used, or discarded. PFOS is no longer manufactured in the United States, and PFOA production has been reduced and will soon be eliminated. More research is needed to fully understand all sources of human exposure, but people are most likely exposed to these compounds by consuming PFC-contaminated water or food, or by using products that contain PFCs. Unlike many other persistent chemicals, PFCs are not stored in body fat. However, PFCs are similar to other persistent chemicals, because the half-life, or the amount of time it takes for 50% of the chemical to leave the human body, for some of these chemicals, is several years. This slow elimination time makes it difficult to determine how changes in lifestyle, diet, or other exposure-related factors influence blood levels.

In animal studies, some PFCs disrupt normal endocrine activity; reduce immune function; cause adverse effects on multiple organs, including the liver and pancreas; and cause developmental problems in rodent offspring exposed in the womb. Data from some human studies suggests that PFCs may also have effects on human health, while other studies have failed to find conclusive links. Additional research in animals and in humans is needed to better understand the potential adverse effects of PFCs for human health.

()

The company W.L. Gore & Associates, the developers of GORE-TEX fabrics, describe the relation of these compounds to the clothing products they manufacture and their move toward greener chemicals.

All GORE-TEX® garments have an ultra-thin treatment called DWR - a durable water repellent polymer - applied to the outermost fabric layer so that water beads up and rolls off rather than soaking in.

State-of-the-art treatments are based on fluorocarbons because they provide a combination of stain and water repellence with high breathability and durability. Treatments that do not contain fluorinated compounds like Silicone or Polyolefine based treatments typically lack one of these properties, either resulting in lower comfort or requiring more frequent water repellent treatment by the consumer. This is why developing a PFC-free DWR is a challenge for the whole industry.

Gore has been using PFOA-free water repellents since 2011. They are made with perfluorinated molecules that have shorter carbon chains (C6 or shorter) than the long-chain structure (C8 to C12) that was typically used in PFOA-related DWRs.

Short-chain repellents (including possible break down products/impurities) have proven to have a better toxicological and environmental profile compared to long-chain chemistry, although they are also stable in the environment.

()

What does the future hold? Even though certain companies are making moves to reduce or eliminate the use of these compounds, there is no quick fix because of the persistence of the chemicals themselves. “In any case, this is unlikely to be the last people will be hearing about PFCs. Even if their production ceased today, they'd still be around in the environment for many decades or longer. And while their production is being phased out in many parts of the world, PFOS production has increased dramatically in China since 2003. Many other PFCs remain in commercial use worldwide.” ()

Connections to Chemistry Concepts (for correlation to course curriculum)

1. Green Chemistry—The April 2003 ChemMatters Teacher’s Guide casts a wide net in relation to the connection of green chemistry to the curriculum, stating, “Since the topic of Green Chemistry is so general, it can connect to virtually anything that might be included in a typical curriculum, depending on the specific process being examined. It clearly and strongly connects to the topics of atoms, reactions, solvents, energy, catalysis, pollution, and renewable and nonrenewable resources, all of which are probably covered in most high school courses.” (ChemMatters Teacher’s Guide. April 2003, p 16)

2. Polarity—The discussion of long-chain fluorinated chemicals includes information about their polarity in contrast to that of water.

3. Bonding—The discussion of long-chain fluorinated chemicals also touches on the idea of bonding, including the strength of particular bonds, such as the carbon–fluorine bond.

Possible Student Misconceptions (to aid teacher in addressing misconceptions)

1. “Green chemistry has nothing to do with my life.” Decisions you make have an impact and can be related to the principles of green chemistry. For example, similar to the author of the ChemMatters article, you decide which shoes, clothing, and other items to purchase. Your decisions could be at least partially based on whether the manufacturers are attempting to follow the principles of green chemistry. Your decisions about disposing of items can also make a difference, for example, are there items you can recycle? Do certain items, such as batteries and electronics, need to be disposed of in a special way? A past ChemMatters article also points out that decisions you and your teacher make in the classroom chemistry laboratory can be related to green chemistry: “What chemicals do we need? (Are they safe? Expensive? Can we use less and still get good results?) What solvent should we use? (Again, is it safe? Will water work as well?) How shall we heat the reaction vessel? (Will it go just as well at room temperature if we wait? Hot plate? Bunsen Burner? Microwave?) And what should we do with the wastes that accumulate? (Down the drain? In the trash can?)” (La Merrill, M.; Parent, K.; Kirchhoff, M. Green Chemistry—Stopping Pollution Before It Starts. ChemMatters 2003, 21 (2), p 7)

2. “A company wouldn’t use something that’s really harmful when they’re making a product.” Decisions companies make have to balance many inputs—what works best to make a product, what is cost-effective, plus possible consideration of what can reduce or eliminate effects on the environment and health. Sometimes what works best is not the most benign compound to use in terms of effects on the environment. We also continue to learn more about the hazards of different compounds, about new compounds to use, and about how to adjust manufacturing processes so they are “greener.”

Anticipating Student Questions (answers to questions students might ask in class)

1. “How can I tell whether something I want to buy is made in a green way?” It can be difficult to tell. For example, for the article, Nolte looked for information about PUMA Re-Suedes to see how many of the 12 Principles of Green Chemistry the shoe design met. She had to include question marks for several of the principles because some information is just not available to consumers. Promotional information included with the product or on the company’s Web site is a natural place to start. Additional internet searches can provide more information but can only go so far.

2. “What is ‘greenwashing’?” Greenwashing is the practice of a company falsely presenting itself and/or its products as being more environmentally-friendly than they actually are. Claiming that something is supposedly “green” is one way to hype a product; we may need to dig deeper to find out what “green” really means in a situation.

3. “Do green products cost more?” Green products can cost more. Sometimes the materials or processes used to make them greener cost more than typical methods. It can vary greatly, depending on the product; cost differences can range from large to small or non-existent. Nolte mentions that the PUMA Re-Suedes cost $70 a pair; this is comparable to other shoes.

In-Class Activities (lesson ideas, including labs & demonstrations)

1. Students could have a taste of making choices based on green chemistry principles by using the laboratory experiment “Green Energy—It’s Your Decision.” They collect data to calculate the efficiency of each of three methods used to heat water (Bunsen burner, an electric hot plate, and a microwave oven). They use information on efficiency, dollar cost, and environmental cost to “make a recommendation on how best to minimize the energy used to heat substances in your school lab.” (Green Energy—It’s Your Decision. ChemMatters 2003, 21 (2), pp 8–9)

2. Students can take a closer look at shoe construction as they transform a used pair of their shoes into a slip-on sandal version using instructions online. They could discuss how this further use of the shoes does/does not support green chemistry principles. ()

3. Print out eye-catching green chemistry bookmarks from the U.S. Environmental Protection Agency for students to use. One side of the bookmark lists the 12 principles of green chemistry. ()

4. A vitamin C clock reaction experiment uses only household materials and leads students to consider the idea of risk, especially in relation to the use of a chemical substance. It addresses the green chemistry principle of using safer starting materials for a process. (“Getting Off to a Safe Start,” Introduction to Green Chemistry: Instructional Activities for Introductory Chemistry. Washington, DC: American Chemical Society, 2002, pp 5–11; see C Clock.pdf)

5. Several examples of interactive displays that illustrate green chemistry to use at educational science expos are described. For example, visitors compare cellulose-based packing peanuts with polystyrene peanuts. ()

Out-of-class Activities and Projects (student research, class projects)

1. Students could research how the PUMA Re-Suede shoes meet the six of the twelve green chemistry principles mentioned in the article and the “Student Questions” section (#8) above. In addition, students could consider any other consumer product, and research and analyze whether/how it meets any of the twelve green chemistry principles.

2. Students and instructors could work together to select a demonstration or experiment currently used in the chemistry classroom and analyze it to suggest ways it could be made “greener.” This could be done with everyday activities outside of the classroom as well. The April 2003 ChemMatters Teacher’s Guide describes one example to modify to make it more green: “We cut our grass in the summer and then dispose of the clippings. Later we go to the local nursery and purchase fertilizer for our garden instead of composting the grass clippings and using them in place of the fertilizer.” (ChemMatters Teacher’s Guide. April 2003, p 16)

3. American Chemical Society (ACS) student chapters on the university level are encouraged to work toward the “Green Chemistry Student Chapter Award” by participating in at least three green chemistry activities during the school year. Multiple ideas for activities are available at and could be adapted for high school chemistry clubs or classes.

References (non-Web-based information sources)

The almost-20-year-old ChemMatters article “PET Recycling” discusses the recycling of polyethylene terephthalate (PET) from used soda bottles to create products such as clothing and shoes. (Plummer, C. PET Recycling. ChemMatters 1994, 12 (3), pp 7–9)

The ChemMatters article “Green Chemistry—Benign by Design” briefly discusses green chemistry, and then describes three products/processes that won Presidential Green Chemistry Challenge Awards. (Ryan, M.A. Green Chemistry—Benign by Design. ChemMatters 1999, 17 (4), pp 9–11)

The ChemMatters article “Green Chemistry—Stopping Pollution Before It Starts” summarizes green chemistry and relates it to decisions made in both a student’s life and in industry. (La Merrill, M.; Parent, K.; Kirchhoff, M. Green Chemistry—Stopping Pollution Before It Starts. ChemMatters 2003, 21 (2), pp 7, 10)

The ChemMatters article “Biomimicry—Where Chemistry Lessons Come Naturally” discusses several examples of how researchers have taken examples from nature as inspiration for greener chemistry methods. (Parent, K.E.; Young, J.L. Biomimicry—Where Chemistry Lessons Come Naturally. ChemMatters 2006, 24 (2), pp 15–17)

A ChemMatters interview with an environmental and sustainability chemist at Nike highlights the role of chemists at the company, particularly in connection with designing and producing “greener” shoes. (Brownlee, C. The Swoosh Goes Green: Interview with John Frazier, Environmental and Sustainability Chemist at Nike. ChemMatters 2008, 26 (3), pp 18–19)

Web Sites for Additional Information (Web-based information sources)

More sites on shoe manufacture and design

Information on the history of how shoes have been made, along with multiple illustrations, is available here: shoes/history/history your shoes/history your shoes.htm.

A “History of the Athletic Shoe” infographic shows many of the steps on the road of the development of shoes, from the earliest shoes to running shoes to minimalist shoes. ()

This company focuses on constructing shoes (mostly by hand) to the individual’s unique specifications rather than mass-produced shoes, but the video provides an overview of the general steps of the shoe-making process. ()

An Engineering and Physical Sciences Research Council (EPSRC) video shows a system that can be used to recycle the materials from old shoes and describes its development. ( - t=49)

A Red Wing Shoes employee describes the making and use of molds to create the soles of shoes. ()

3D printing is mentioned in this article as a method for producing shoe features that would normally not be able to be easily manufactured using ordinary processes. ()

A blogger describes a project-based learning experience centering on shoe design and the ability to view and solve problems in a new way. ()

The Tread Project is described as “a 7 week experimental design studio which aims to educate and inspire students with creative problem solving skills through the vehicle of footwear design.” ()

Learn about high school art students who entered a national competition, designing Vans-brand shoes. ()

More sites on “green” shoes

The Nike company discusses its choices in materials and design, and their relation to green chemistry. ()

Artificial “eco-leather” that can be used in shoe manufacture is in development. The professor mentioned at this site eventually won a 2013 Presidential Green Chemistry Challenge Award for his work. ()

A paper for a university-level course “Sustainability Science” provides a “Sustainability Assessment of Nike Shoes.” ()

The PUMA company uses packaging for its shoes and products that fits the green chemistry mindset. Instead of a typical shoebox, they use a reusable shoe bag. ()

More sites on green chemistry

The American Chemical Society Green Chemistry Institute quotes the twelve principles of green chemistry as laid out by Anastas and Warner. Each principle is then linked to a short contribution by a green chemistry expert; these pieces were published once each month in 2013. ()

The American Chemical Society Green Chemistry Institute offers downloadable “Green Chemistry Pocket Guides” that concisely summarize green chemistry and its guiding principles. One guide is designed for scientists, science students, and professors, the other for the general public. ()

The U.S. Environmental Protection Agency has produced the video “Green Chemistry for a Sustainable and Healthy Economy.” It describes green chemistry, examples of how and where it has been used, and its benefits. ()

A listing of the Presidential Green Chemistry Challenge Award winners is available online, along with technology summaries and for some of the winners, podcasts. ()

For a more advanced reader, three green chemistry case studies help to link green chemistry technology to the business side of the developments. The case studies focus on 2012 winners of the Presidential Green Chemistry Challenge Awards. ()

A Chemical & Engineering News article “Honoring Green Chemistry” highlights the 2013 winners of the Presidential Green Chemistry Challenge Awards. One of the winners, Richard P. Wool, has made materials useful to shoe manufacture. ()

More sites on perfluorinated compounds

The National Institute of Environmental Health Services offers a fact sheet on perfluorinated chemicals. It includes information on what they are, studies that are being done, and how to avoid exposure. ()

A Huffington Post article discusses research on potential effects that perfluorinated compounds can have on the human body. ()

A Bloomberg Businessweek article focuses on plans shoe and clothing manufacturers have made to eliminate the use of certain chemicals. Perfluorinated compounds are mentioned. ()

More Web sites on Teacher Information and Lesson Plans (sites geared specifically to teachers)

A 2010 ACS/NSTA Web seminar focused on green chemistry. Presenters Michael Tinnesand and Barbara Sitzman described how and why green chemistry can be integrated into the classroom, with examples of activities and other resources. ()

Beyond Benign offers a collection of high school lesson plans centering on green chemistry. ()

The University of Oregon has a database of chemistry education materials for teaching green chemistry, called “Greener Education Materials for Chemists” (GEMs). The database is searchable by keyword and/or category. ()

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The references below can be found on the

ChemMatters 30-year CD (which includes all articles

published during the years 1983 through April 2013

and all available Teacher’s Guides). The CD is in

production and will be available from the American Chemical Society at this site:

.

Selected articles and the complete set of Teacher’s Guides for all issues from the past three

years are also available free online on the same site.

(The complete set of ChemMatters articles and Teacher’s Guides are available on the 30-year CD for

all past issues, (up to April 2013.)

 

Some of the more recent articles (2002 forward) may also be available online at the link above. Simply click on the “Past Issues” button directly below the “M” in the ChemMatters logo at the top of the Web page. If the article is available online, you will find it there.

30 Years of ChemMatters !

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